Hydrolysis of cellulosic fines in primary clarified sludge of paper mills and the addition of a surfactant to increase the yield

The present application is a non-provisional of, and claims benefit of priority under 35 U.S.C. §119(e) from U.S. Provisional Patent Application Ser. No. 61/792,793, filed Mar. 15, 2014, the entirety of which is expressly incorporated herein by reference.

Not Applicable

This invention relates to processing of cellulosic solid waste from paper related industries for extraction of fermentable sugars.

Lignocellulosic materials are excellent sources for energy products, platform chemicals and bioplastics. Sugars produced by the degradation of carbohydrate polymers can be fermented into ethanol and butanol as energy sources. Sugars and cellulose degradation compounds can serve as platform chemicals in the production of bulk chemicals and they can also be used as feedstocks for microbial production of plastics such as polyhydrolxyalkanoates.

See, U.S. Pat. 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Each of the foregoing references is expressly incorporated herein by reference it their entirety.

Paper mills, especially those recycling old cardboard containers (OCC) produce large quantities of fiber fragments which pass through into the waste stream. These fines are composed primarily of cellulose and hemicellulose (amorphous short chain polymers of substituted hexoses and pentoses). They are the source of substantial bioburden due to their long time decay in the environment. Since they contribute substantially to the oxygen demand in the effluents, they are typically separated and sent to landfills by the paper mills. Current landfilling costs are nearly $60/ton, and thus disposal costs to the paper mills are to the tune of $1.5 million/year based on typical sludge production at an average size paper mills in NY at 100 tons/day.

These costs are projected to increase substantially in the future due to the pressure on landfill space. Therefore there is an acute need to divert the wastes, perhaps extracting value through products which not only are marketable but also reduce the landfill volumes.

The waste stream from recycled paper mills contains cellulosic fines and also particles of mineral origin, typically clay or calcium carbonate from the fillers and coatings used in the waste paper. The cellulosic fines are easily hydrolyzable by either acid or enzymatic processes. In the enzymatic process, a cocktail of cellulose enzymes acts progressively and sequentially to open up the cellulose crystalline structure and depolymerize it, producing monomeric sugars. The sugars are primarily glucose and certain other common hexoses which are fermentable into ethanol, butanol or other advanced energy products. Microbial fermentation can also lead to bioplastics such as polyhydroxyalkanoates.

A sample set of fines rejected from a recycled paper mill was obtained. The composition is presented in Table 1 below.

Though the properties of sludge differ not only for different mills but also at different times at same mill, Table 1 is exemplary of possible conditions. The pH of sludge varies between 6 and 8. Ash content is very high for recycled papermills. The short fibers (mainly cellulose fibers) go to belt filter and then to screw press. In general, the PCS contains very high levels of dry solids because it is rich in hydrophobic fibers. To summarize, PCS is a mixture of cellulose fibre (40-65% of dry solids), printing inks and mineral components (25-40% dry solids: kaolin, talc and calcium carbonate). Due to high fiber content PCS has large amount of carbon (around 50% C dry solids) and mineral matter (clay and calcium carbonate, 5-25% dry solids).

The present technology processes a waste stream comprising cellulosic fines, e.g., from recycled packaging paper mills, into a stream of fermentable sugars. These fermentable sugars may be fermented to yield bioethanol which is of value as a fuel, for production of biodiesel and other alkoxy esters, and/or manufacturers of other products such as bioplastics such as polyhydroxy alkanoates.

According to a preferred embodiment, a process is provided to:

(a) hydrolyze the cellulosic fines found in recycled paper mill waste streams using a commercially available cellulose enzyme formulation;

(b) increase the enzymatic hydrolysis yield by shielding the inert components of the waste stream using a surfactant; and

(c) optimize the surfactant with respect to its composition (anionic, non-ionic or cationic) and dosage.

Recycled containerboard and linerboard paper mills reject significant amounts of cellulosic fines into their waste stream which are eventually landfilled at a cost to the manufacturer and also present a load on the environment. However, it is possible to digest the cellulosic portions of the rejects by enzymatic hydrolysis and thus produce sugars in their monomeric forms. The resulting sugar solutions can be fermented into biofuels such as ethanol and butanol, or processed into biomaterials such as polyhydroxy-alkanoates. The enzymes, however, may have a competitive binding affinity for inorganic particulates, resulting in a non-specific absorption of some or all types of enzymes to the particles. Indeed, similar high surface area particles are used in the purification of similar enzymes. Therefore, in the presence of inorganic particles, such as precipitated calcium carbonate (PCC), the activity and bioavailability of the enzymes may be substantially reduced.

It has been found that surfactants are able to coat the inorganic particulates and otherwise reduce binding of the hydrolytic enzymes, leading to a significant increase in activity, thus saving cost and increasing efficiency. It has been found that effective surfactants do not also block binding or biological activity of the enzymes for the cellulosic particles and components of the solution.

Cationic, non-ionic and anionic surfactants were tested at various dosages. A non-ionic surfactant, Tween 80 (polysorbate 80) was better than the tested cationic and anionic surfactants.

The inorganic particles may be separated from the waste stream, and used as animal bedding or the like.

Some investigators have suggested the use of anaerobic fermentation as a means to degrade and make use of the organic components in the waste stream, but due to presence of large amount of calcium carbonate, kaolin and other fillers, they give rise to problems such as scaling of biomass, reactors and pipes, reduced specific methanogenic activity and loss of buffer capacity, and essential nutrients for anaerobic degradation.

According of the present technology, hydrolysis the cellulosic constituent of PCS and screw press sludge and produce high value fermentable sugars, which permit efficient fermentation to ethanol, and also production of plastics and other useful materials.

The present technology avoids use of membranes or separation tanks to separate inhibitors and thus lowers the cost of separation. It also produces bi-products such as low quality fillers that can be sold to recycled paper mills or animal bedding processors. Because both the organic and inorganic components are separated and made available for downstream use, the amount of burden on landfill is substantially reduced.

Commercially available hydrolysis enzymes include Cellic® HTec3, a concentrated hemicellulase that works alone or in combination with Cellic® CTec3 cellulase enzyme from Novozymes (Denmark).

See:

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N., et al. “Enzymatic hydrolysis of cellulose and various pretreated wood fractions.” Biotechnology and bioengineering 24.6 (1982): 1389-1402; Khodaverdi, Mandi, et al. “Kinetic modeling of rapid enzymatic hydrolysis of crystalline cellulose after pretreatment by NMMO.” Journal of industrial microbiology & biotechnology (2012): 1-10; Obama, Patrick, et al. “Combination of enzymatic hydrolysis and ethanol organosolv pretreatments: Effect on lignin structures, delignification yields and cellulose-to-glucose conversion.” Bioresource Technology (2012); Wiman, Magnus, et al. “Cellulose accessibility determines the rate of enzymatic hydrolysis of steam-pretreated spruce.” Bioresource Technology (2012); Elliston, Adam, et al. “High concentrations of cellulosic ethanol achieved by fed batch semi simultaneous saccharification and fermentation of waste-paper.” Bioresource Technology (2013); Kinnarinen, Teemu, et al. “Effect of mixing on enzymatic hydrolysis of cardboard waste: Saccharification yield and subsequent separation of the solid residue using a pressure filter.” Bioresource technology (2012); Wang, Lei, Richard Templer, and Richard J. Murphy. “High-solids loading enzymatic hydrolysis of waste papers for biofuel production.” Applied Energy (2012); Li, Sujing, Xiaonan Zhang, and John M. Andresen. “Production of fermentable sugars from enzymatic hydrolysis of pretreated municipal solid waste after autoclave process.” Fuel 92.1 (2012): 84-88; Dubey, Alok Kumar, et al. “Bioethanol production from waste paper acid pretreated hydrolyzate with xylose fermenting Pichia stipitis .” Carbohydrate Polymers (2012); Kinnarinen, Teemu, et al. “Solid-liquid separation of hydrolysates obtained from enzymatic hydrolysis of cardboard waste.” Industrial Crops and Products 38 (2012): 72-80; Nørholm, Nanna Dreyer, Jan Larsen, and Frank Krogh Iversen. “Non-pressurised pretreatment, enzymatic hydrolysis and fermentation of waste fractions.” U.S. patent application Ser. No. 13/405,262; Das, Arpan, et al. “Production of Cellulolytic Enzymes by Aspergillus fumigatus ABK9 in Wheat Bran-Rice Straw Mixed Substrate and Use of Cocktail Enzymes for Deinking of Waste Office Paper Pulp.” Bioresource technology (2012); Chen, Hui, et al. “Enzymatic Hydrolysis of Recovered Office Printing Paper with Low Enzyme Dosages to Produce Fermentable Sugars.” Applied biochemistry and biotechnology (2012): 1-16; Yan, Shoubao, et al. “Fed batch enzymatic saccharification of food waste improves the sugar concentration in the hydrolysates and eventually the ethanol fermentation by Saccharomyces cerevisiae H058.” Brazilian Archives of Biology and Technology 55.2 (2012): 183-192; Arora, Anju, et al. “Effect of Formic Acid and Furfural on the Enzymatic Hydrolysis of Cellulose Powder and Dilute Acid-Pretreated Poplar Hydrolysates.” ACS Sustainable Chemistry & Engineering 1.1 (2012): 23-28; Wang, Lei, et al. “Technology performance and economic feasibility of bioethanol production from various waste papers.” Energy & Environmental Science 5.2 (2012): 5717-5730; Vazana, Yael, et al. “Designer Cellulosomes for Enhanced Hydrolysis of Cellulosic Substrates.” Cellulases (2012): 429; Van Dyk, J. S., and B. I. Pletschke. “A review of lignocellulose bioconversion using enzymatic hydrolysis and synergistic cooperation between enzymes-Factors affecting enzymes, conversion and synergy.” Biotechnology Advances (2012); Menind, A., et al. “Pretreatment and usage of pulp and paper industry residues for fuels production and their energetic potential.” International Scientific Conference Biosystems Engineering, Tartu, Estonia, 10-11 May 2012. Vol. 10. No. Special Issue I. Estonian Research Institute of Agriculture, 2012; Han, Lirong, et al. “Alkali pretreated of wheat straw and its enzymatic hydrolysis.” Brazilian Journal of Microbiology 43.1 (2012): 53-61; Holm, Jana, et al. “Pretreatment of fibre sludge in ionic liquids followed by enzyme and acid catalysed hydrolysis.” Catalysis Today (2012),

each of which is expressly incorporated herein by reference.

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FIG. 1 shows hydrolysis yield of synthetic substrate of varying composition after addition of different concentration of surfactant (Tween80) and enzyme.

FIG. 2 shows hydrolysis yield of synthetic substrate of Calcium Carbonate (15%) after addition of different concentration of surfactant (Tween80) and enzyme.

FIG. 3 shows hydrolysis yield of screw press fines with addition of different concentrations of surfactant (Tween 80)

Hydrolysis experiments were conducted on two different feedstocks. The first was a simulated waste feedstock, consisting of a sample of unbleached kraft softwood pulp (UBSWKP) that is typical of repulped old corrugated containerboard stocks (OCC). The second was an actual reject fines waste stream from a recycled paper board mill. (Supplied by Minimill LLC, Dewitt N.Y. in conjunction with Greenpak LLC, Niagara Falls N.Y.). The reject stream consisted of cellulosic fines (35%) with the remainder as ash-producing constituents. The non-cellulosic portion contains kaolin and precipitated calcium carbonate fillers from the waste paper and smaller amounts of plastic and other residues.

The non-cellulosic portion of the feedstock acts a competitor for enzyme adsorption, and reduces the net yield and productivity of the hydrolysis per unit enzyme reactant. This leads to increased costs and inefficiencies in the hydrolysis process.

Table 2 below shows the enzymatic hydrolysis yields of a sample of waste fines solids from a recycled paper mill. Although the yields are relatively low, an increase would be expected upon routine optimization with respect to enzyme dosages.

The present approach to resolve this problem is to preferentially or selectively cover the inorganic components with a suitable surfactant so that enzyme binding and action is localized to the cellulosic components. For this purpose, cationic, non-ionic and anionic surfactants were tested at different dosages.

Results are shown for the case of the nonionic surfactant. The ionic surfactants tested were not seen as being as effective as the nonionic surfactant.

A pulp sample (unbleached kraft softwood pulp) was chosen as a model of the OCC pulp. FIG. 1 below shows the hydrolysis yield when a mixture of surfactant and enzyme was applied to this sample mixed with fillers. Hydrolysis yield was defined as the mass of cellulose dissolved (by the action of the enzyme) to the original (oven dry) mass of the sample. Different dosages of the enzyme are represented on the abscissa by FPU. The surfactant added was Tween 80, a polysorbate nonionic carbohydrate based detergent.

FIG. 1 shows that the addition of the surfactant increases the hydrolysis yield when the enzyme activity is greater than 10 FPUs. The untreated calcium carbonate filler suppresses enzyme hydrolysis, whereas the kaolin filler is more benign to the action of the enzymes. FIG. 2 shows the hydrolysis yield as a function of dosage of the surfactant with enzyme loading chosen as 20 FPUs. The maximum effect surfactant dosage appears to be close to 7% based on the oven dry weight of the biomass. FIG. 3 shows that the hydrolysis yield of mill waste rejects containing fines also increases with the addition of the same nonionic detergent.

The numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.